Kinetics of Thermal Isomerization of meso-Diethyl 2,3-Dicyano-2,3-Diphenyl Succinate and the EPR Spectra of the Intermediate in Melten State

Abstract

Abstract: The kinetics were studied for the thermal isomerization of meso-diethyl 2,3-dicyano-2,3-di (p-Xsubstituted phenyl) succinates (X = H) in melten state and the EPRspectra of the intermediates (X = OCH₃, CH₃, H, Cl, NO₂) were observed.The central carbon-carbon bond of the five isomers was homolysed to give ethyl α-cyano-α-ethoxycarbonyl-p-substituted benzyl radicals.The structures of the intermediates were determined by compute simulation.The kinetic results indicate that the equilibrium constant Kreduced as the rise of the reaction temperature.The active parameters were found to be ΔH_dl-meao= - 18.02 kJ/mol, ΔS_dl-meao= - 26.51 J/mol·K, ΔH^≠ = 151.78 kJ/mol, ΔS^≠ = 71.64 J/mol·K.dl-Isomer is more stable than the corresponding meso-iscmer.

Key words: Meso-diethyl 2, 3-dicyano-2, 3-di(p-X substituted phenyl) succinate, Melten state, Thermal isomeriztion, Kinetics, EPR

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QI Chen-Ze, JIA Zhi-Sheng, YANG Di-Lun . Kinetics of Thermal Isomerization of meso-Diethyl 2,3-Dicyano-2,3-Diphenyl Succinate and the EPR Spectra of the Intermediate in Melten State[J]. Chem. J. Chinese Universities, 1993, 14(3): 402.

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Kinetics of Thermal Isomerization of meso-Diethyl 2,3-Dicyano-2,3-Diphenyl Succinate and the EPR Spectra of the Intermediate in Melten State

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